JP5620086B2 - Modified polyhedral polysiloxane and composition containing the modified - Google Patents

Description

  The present invention relates to a modified polyhedral polysiloxane having excellent moldability, transparency, heat resistance, light resistance and the like, and excellent impact resistance, and a composition containing the modified body.

  Polysiloxane composition is excellent in heat resistance, cold resistance, weather resistance, light resistance, chemical stability, electrical properties, flame resistance, water resistance, transparency, colorability, non-adhesiveness, non-corrosion It is used in various industries. Among them, a composition composed of polysiloxane having a polyhedral structure is known to exhibit further excellent heat resistance, light resistance, chemical stability, low dielectric property, etc. from its specific chemical structure. .

  However, polyhedral polysiloxanes are generally polyfunctional and solid compounds, are difficult to control, and have poor handling and molding processability, making them difficult to materialize. For example, although a hydrosilylation curable composition using a functional group-containing polysiloxane is disclosed (Non-patent Document 1), the polyhedral polysiloxane that is a starting material is a polyfunctional solid material in the corresponding technology. Therefore, there is room for further improvement in the control of the curing reaction, handling properties and molding processability.

  In addition to this, curable compositions (Patent Documents 1 to 3) using polysiloxanes having a polyhedral skeleton containing an epoxy group or a phenyl group are disclosed, but coloring under heating is observed under high temperature conditions. The properties of the polysiloxane composition are not fully utilized.

  As described above, disclosure of a material using a polysiloxane compound having a polyhedral skeleton can be seen, but no example of a liquid compound having sufficient characteristics and excellent handling properties and molding processability has been found.

  Moreover, about the curable resin using polyhedral polysiloxane, there exists a subject that intensity | strength is insufficient in the hardened | cured material when it hardens | cures and it is weak in impact resistance.

  As described above, there has been a demand for the development of a material capable of solving the problems of sufficiently expressing the characteristics of polyhedral polysiloxane, being excellent in handling and molding processability, and being weak in impact resistance of a cured product.

Special table 2004-529984 JP 2004-359933 A JP 2006-22207 A

J. et al. Am. Chem. Soc. 1998, 120, 8380-8391

  In order to solve the above problems, the present invention provides a modified polyhedral polysiloxane having excellent molding processability, transparency, heat resistance, light resistance, etc., and excellent impact resistance, and a composition containing the modified body. The purpose is to do.

As a result of intensive studies to solve the above problems, the present inventors have found that the problems are solved by having the following configuration. That is, the present invention has the following configuration.

1). formula
[XR ₂ SiO—SiO _3/2 ] _a [XR ₂ SiO— (R ₂ SiO) _m —SiO _3/2 ] _b [R ′ — (R ₂ SiO) _n —SiO _3/2 ] _c (a to c Is an integer of 0 or 1 or more, a + b + c is an integer of 6 to 24, b + c is an integer of 1 or more, m, n is an integer of 1 or more; R is an alkyl group or an aryl group, They may be the same or different from each other; R ′ is another polyhedral polysiloxane; X is a hydrogen atom or an alkenyl group, and may be the same or different). A polyhedral polysiloxane-modified product obtained by hydrosilylating a polyhedral polysiloxane-based compound (a) with a compound (b) containing a hydrosilyl group or an alkenyl group.

  2). The modified polyhedral polysiloxane according to 1), which is liquid at 20 ° C.

  3). The modified polyhedral polysiloxane according to 1) or 2), which has at least three hydrosilyl groups or alkenyl groups in the molecule.

  4). The modified polyhedral polysiloxane according to any one of 1) to 3), wherein the compound (b) containing a hydrosilyl group or an alkenyl group is a siloxane compound containing a hydrosilyl group or an alkenyl group. .

  5). Any one of 1) to 4), wherein the polyhedral polysiloxane compound (a) is obtained by reacting a silicate having a polyhedral structure with a mixture of monochlorosilane and dichlorosilane. The polyhedral polysiloxane modified product.

  6). A polysiloxane-based composition comprising the modified polyhedral polysiloxane according to any one of 1) to 5).

  7). 6. The polysiloxane composition according to 6), which contains a curing agent.

  8). The polysiloxane composition according to 7), wherein the curing agent contains at least one alkenyl group or hydrosilyl group.

  9). The polysiloxane composition according to 79 or 8), wherein the curing agent contains polysiloxane having a molecular weight of less than 1000 as an essential component.

  10). 6. The polysiloxane composition according to any one of 6) to 9), comprising a hydrosilylation catalyst.

  11). Hardened | cured material obtained using the polysiloxane type composition of any one of 6) -10).

  ADVANTAGE OF THE INVENTION According to this invention, the polyhedral polysiloxane modified body which is excellent in molding processability, transparency, heat resistance, light resistance etc., and is excellent in impact resistance, and the composition containing this modified body can be provided.

<Polyhedral polysiloxane compound (a)>
The polyhedral polysiloxane compound (a) is composed of an oligomer having a siloxane bond in the side chain or two or more polyhedral polysiloxanes linked by a siloxane bond, and represented by the following formula (1): It consists of siloxane units represented.

  This polyhedral polysiloxane compound (a) can be made into a liquid component by introducing a siloxane bond into the side chain or connecting it with a siloxane bond.

[XR ₂ SiO—SiO _3/2 ] _a [XR ₂ SiO— (R ₂ SiO) _m —SiO _3/2 ] _b [R ′ — (R ₂ SiO) _n —SiO _3/2 ] _c (1)
(A to c are integers of 0 or 1 or more, a + b + c is an integer of 6 to 24, b + c is an integer of 1 or more, m and n are integers of 1 or more, R is an alkyl group and an aryl group, In the case where there are plural groups, they may be the same or different from each other, R ′ is another polyhedral polysiloxane, X is a hydrogen atom or an alkenyl group, and may be the same or different.) .

  X is a substituent that modifies the compound (b) containing a hydrosilyl group or alkenyl group described later by a hydrosilylation reaction in the presence of a hydrosilylation catalyst, and is a hydrogen atom or an alkenyl group.

  R is an alkyl group or an aryl group, and when there are a plurality of each, they may be the same or different. R in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

(1) In the formula, siloxane bonding sites (R ₂ SiO) _m and (R ₂ SiO) _n are components useful for liquefying a polyhedral polysiloxane compound, and each of m and n is 1 or more. Although it will not specifically limit if it is an integer, it is desirable that it is an integer of 1-20. The siloxane bonding site is important for adjusting the physical properties of the polyhedral polysiloxane and the resulting cured product in the present invention. By adjusting the m number, the crosslinking density is adjusted, the film property, the leveling property, Brittleness can be improved.

<Method for producing polyhedral polysiloxane compound (a)>
In the present invention, in order to obtain a desired polyhedral polysiloxane compound (a), a silicate having a polyhedral structure may be used as a precursor.

  A method for synthesizing a silicate having a polyhedral structure is not particularly limited, and the silicate can be synthesized using a known method. Specifically, a method in which tetraalkoxysilane is hydrolytically condensed in the presence of a base such as quaternary ammonium hydroxide can be used.

  Examples of tetraalkoxysilane include tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane. Examples of the quaternary ammonium hydroxide include 2-hydroxyethyltrimethylammonium hydroxide and tetramethylammonium hydroxide. In the present invention, it is possible to obtain a silicate having a similar polyhedral structure from a silica-containing substance such as silica or rice husk instead of tetraalkoxylane.

  The desired polyhedral polysiloxane compound (a) can be obtained by silylating the silicate having the polyhedral structure with chlorosilane.

  Chlorosilane is not particularly limited as long as the product after silylation is obtained as a compound represented by the above formula (1).

  Although the addition amount of chlorosilane is not particularly limited, it is used so that the total number of chlorine atoms in chlorosilane is 0.5 to 10 with respect to one silicon atom of silicate having a polyhedral structure as a precursor. It is preferable that it is 0.8-5.

  In the method for producing a polyhedral polysiloxane compound (a) according to the present invention, the chlorosilane mole added by using dichlorosilane in combination with monochlorosilane during the silylation, compared to when using monochlorosilane alone. Since the number can be reduced, a polyhedral polysiloxane compound can be obtained more effectively.

  Examples of monochlorosilane include dimethylhydrochlorosilane, methylphenylhydrochlorosilane, diphenylhydrochlorosilane, dimethylvinylchlorosilane, methylphenylvinylchlorosilane, and diphenylvinylchlorosilane.

  Examples of dichlorosilane include dimethyldichlorosilane, methylphenyldichlorosilane, and diphenyldichlorosilane.

  As a ratio of the addition amount of monochlorosilane and dichlorosilane, 0.1 to 4 mol, further 0.4 to 3 mol, particularly 0.6 to 2.5 mol of dichlorosilane with respect to 8 mol of monochlorosilane. It is preferable to use in the range. If the amount of chlorosilane added is large, a siloxane compound that does not include a polyhedral structure in the chemical structure may be produced as a by-product, and if it is too small, solids may remain in the product or gelate.

<Compound (b) containing hydrosilyl group or alkenyl group>
The hydrosilyl group or alkenyl group-containing compound (b) in the present invention is a compound containing at least one hydrosilyl group or alkenyl group in the molecule, preferably 2 or more. From the viewpoint of transparency, heat resistance, and light resistance, it is preferably a siloxane compound having a hydrosilyl group or alkenyl group, and further, a cyclic siloxane having a hydrosilyl group or alkenyl group, or a straight chain having a hydrosilyl group or alkenyl group. A siloxane is preferred.

  The hydrosilyl group or alkenyl group-containing compound (b) in the present invention may be used alone or in combination of two or more.

  As the linear siloxane having an alkenyl group, a copolymer of a dimethylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, a copolymer of a diphenylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, Examples thereof include a copolymer of a methylphenylsiloxane unit, a methylvinylsiloxane unit, and a terminal trimethylsiloxy unit, and a polysiloxane whose terminal is blocked with a dimethylvinylsilyl group.

  Examples of the cyclic siloxane having an alkenyl group include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3, 5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, 3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11 -Hexamethylcyclosiloxane and the like are exemplified.

  Specific examples of the linear siloxane having a hydrosilyl group include a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit, and a terminal trimethylsiloxy unit, a diphenylsiloxane unit, a methylhydrogensiloxane unit, and a terminal trimethylsiloxy unit. Copolymer of methylphenylsiloxane unit, methylhydrogensiloxane unit and terminal trimethylsiloxy unit, polysiloxane end-capped with dimethylhydrogensilyl group, 1,1,3,3-tetramethyl Examples include disiloxane.

  Specific examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trimethyl. Hydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 -Trihydrogen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11- Hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane and the like are exemplified.

  As the cyclic siloxane in the present invention, specifically from the viewpoint of industrial availability and reactivity when modified, or heat resistance, light resistance, strength, etc. of the obtained cured product, for example, 1, 3, 5, 7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane can be preferably used.

  In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom, a vinyl group and a methyl group.

<Hydrosilylation catalyst>
In the present invention, a hydrosilylation catalyst can be used when synthesizing a polyhedral polysiloxane-modified product and curing a polysiloxane composition using the compound.

  As the hydrosilylation catalyst used in the present invention, a known hydrosilylation catalyst can be used, and there is no particular limitation.

Specifically, for example, a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum; a platinum-vinylsiloxane complex, for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex, such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex, such as Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer) , Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al U.S. Patent Platinum is described in the 3220972 Pat Arcola - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

<Modified polyhedral polysiloxane>
The modified polyhedral polysiloxane can be synthesized by a hydrosilylation reaction between the polyhedral polysiloxane compound (a) and the compound (b) having a hydrosilyl group or an alkenyl group in the presence of a hydrosilylation catalyst.

  By carrying out the hydrosilylation reaction, it becomes possible to impart higher heat resistance, light resistance and impact resistance to the polyhedral polysiloxane modified product or the cured product obtained using the polyhedral polysiloxane modified product. . At this time, all of the alkenyl groups or hydrosilyl groups of the modified polyhedral polysiloxane do not need to react and may partially remain.

  The addition amount of the compound (b) having a hydrosilyl group or alkenyl group is such that the number of hydrogen atoms or alkenyl groups directly bonded to Si atoms is one per number of alkenyl groups or hydrosilyl groups of the polyhedral polysiloxane compound (a). It is preferable to use 2.5 to 20 pieces. When the addition amount is small, gelation proceeds due to a crosslinking reaction, so that the handleability of the polyhedral polysiloxane modified product is inferior, and when it is too large, the physical properties of the cured product may be adversely affected.

  In addition, when synthesizing the polyhedral polysiloxane modified product, an excess amount of the compound (b) having a hydrosilyl group or alkenyl group is present, for example, having an unreacted hydrosilyl group or alkenyl group under reduced pressure and heating conditions. It is preferable to remove the compound (b).

The addition amount of the hydrosilylation catalyst used in the synthesis of the modified polyhedral polysiloxane is not particularly limited, but is, for example, in the range of 10 ⁻¹ to 10 ⁻¹⁰ mol relative to 1 mol of the alkenyl group of the polyhedral polysiloxane compound. It is good to use in. Preferably, it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. If there are too many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light at short wavelengths, so the light resistance of the resulting cured product may be reduced, and the cured product may also foam. . Moreover, when there are too few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

  The polyhedral polysiloxane modified product thus obtained can ensure compatibility with various compounds, particularly siloxane compounds, and further, since a hydrosilyl group or an alkenyl group is introduced into the molecule, It becomes possible to react with a compound having an alkenyl or hydrosilyl group. Specifically, a cured product can be obtained by reacting with a curing agent described later.

  At this time, it is preferable that at least three hydrosilyl groups or alkenyl groups in the modified polyhedral polysiloxane are contained in the molecule. If the number of hydrosilyl groups or alkenyl groups is less than 3, the strength of the resulting cured product may be insufficient.

  The modified polyhedral polysiloxane in the present invention can be liquid at a temperature of 20 ° C. It is preferable that the modified polyhedral structure polysiloxane is in a liquid form because of excellent handling properties.

<Curing agent>
The curing agent in the present invention is not particularly limited as long as it has at least one alkenyl group or hydrosilyl group in the molecule. From the viewpoint of imparting impact strength, polysiloxane having a molecular weight of less than 1000 is an essential component. It is preferable to do. By using the one having a molecular weight of less than 1000, specifically, for example, an effect of improving impact strength is seen.

  The curing agent in the present invention preferably contains at least two alkenyl groups or hydrosilyl groups in one molecule, and polysiloxane having an alkenyl group or hydrosilyl group is preferred.

  Further, from the viewpoint of heat resistance and light resistance, linear polysiloxanes having alkenyl groups or hydrosilyl groups, cyclic siloxanes having alkenyl groups or hydrosilyl groups, and polysiloxanes having alkenyl groups or hydrosilyl groups at the molecular ends are preferred. As an example.

  Further, from the viewpoint of further heat resistance and light resistance, the substituent other than the alkenyl group or hydrosilyl group in the curing agent in the present invention is preferably a methyl group or a hydrogen atom. These polysiloxanes having alkenyl groups or hydrosilyl groups may be used alone or in combination of two or more.

  Specific examples of the linear siloxane having an alkenyl group include a copolymer of a dimethylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit. Examples thereof include a polymer, a copolymer of a methylphenylsiloxane unit, a methylvinylsiloxane unit, and a terminal trimethylsiloxy unit, and a polysiloxane whose end is blocked with a dimethylvinylsilyl group.

  Specific examples of the cyclic siloxane having an alkenyl group include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1 , 3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7, 9,11-hexamethylcyclosiloxane and the like are exemplified.

Specific examples of the polysiloxane having an alkenyl group at the molecular end include the polysiloxane whose end is blocked by the dimethylalkenyl group exemplified above, a dimethylalkenylsiloxane unit and a SiO ₂ unit, a SiO _3/2 unit, and a SiO unit. Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group.

  Specific examples of the linear siloxane having a hydrosilyl group include a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit, and a terminal trimethylsiloxy unit, a diphenylsiloxane unit, a methylhydrogensiloxane unit, and a terminal trimethylsiloxy unit. And a copolymer of a methylphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a polysiloxane whose ends are blocked with a dimethylhydrogensilyl group.

  Specific examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trimethyl. Examples include hydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane.

Specific examples of the polysiloxane having a hydrosilyl group at the molecular end include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups exemplified above, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _1/2 units And a polysiloxane composed of at least one siloxane unit selected from the group consisting of SiO ₂ units, SiO _3/2 units, and SiO units.

  In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom, a vinyl group and a methyl group.

  Although the addition amount of the curing agent can be variously set, it may be added at a ratio of 0.3 to 5, preferably 0.5 to 3, hydrogen atoms directly bonded to Si atoms per alkenyl group. desirable. If the ratio of the alkenyl group is too small, appearance defects due to foaming and the like are likely to occur, and if too large, the physical properties of the cured product may be adversely affected.

  As the curing agent, polysiloxane having a molecular weight of less than 1000 is preferably used. The polysiloxane having a molecular weight of less than 1000 is preferably used in the range of 5 to 55% by weight, more preferably 10 to 50% by weight, based on the synthesis of the cured product (100% by weight). If the polysiloxane having a molecular weight of less than 1000 is too much, the low stress becomes insufficient and may cause cracks, and if it is too little, the strength against impact may be reduced.

<Curing retarder>
The curing retarder is a component for improving the storage stability of the polysiloxane composition of the present invention or adjusting the reactivity of the hydrosilylation reaction during the curing process. In the present invention, as the retarder, known compounds used in addition-type curable compositions with hydrosilylation catalysts can be used. Specifically, compounds containing aliphatic unsaturated bonds, organophosphorus compounds , Organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the like. These may be used alone or in combination of two or more.

  Specific examples of the compound containing an aliphatic unsaturated bond include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 3,5-dimethyl-1- Examples thereof include propargyl alcohols such as hexyn-3-ol and 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate, and the like.

  Specific examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

  Specific examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Specific examples of nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, and N, N-dibutyl. -1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, 2,2 Examples include '-bipyridine.

  Specific examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like.

  Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferred curing retarders.

The addition amount of the curing retarder is not particularly limited, but is preferably used in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 100 mol, with respect to 1 mol of the hydrosilylation catalyst. preferable. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

<Polysiloxane composition>
The polysiloxane composition of the present invention can be obtained by adding a curing agent and, if necessary, a hydrosilylation catalyst, a curing retarder, and an adhesion promoter to the modified polyhedral polysiloxane. The polysiloxane composition of the present invention can be handled as a transparent liquid resin composition.

  By making it into a liquid composition, it can be suitably used as a coating agent or a sealing agent by being poured into a package, a substrate or the like, and heated and cured. In addition, the composition can be poured into a mold and heated to obtain a cured product having high transparency, heat resistance, light resistance, impact resistance, workability, and the like.

  As a cured product obtained by curing a liquid polysiloxane composition, for example, a 1 mm-thick cured product having a transmittance of 75% or more with 700 nm light can be obtained. In addition, since the heat resistance is good, it is possible to obtain a cured product with a small decrease in transmittance even when exposed to high temperatures. In addition, it is preferable that the polyhedral polysiloxane-modified product is in liquid form, because the polysiloxane composition of the present invention can be easily obtained in liquid form.

  When adding temperature when making it harden | cure, Preferably it is 30-400 degreeC, More preferably, it is 40-250 degreeC. If the curing temperature is too high, the resulting cured product tends to have poor appearance, and if it is too low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, for example, by raising the curing temperature stepwise such as 70 ° C., 120 ° C., 150 ° C., and 180 ° C., a good cured product can be obtained.

  In the present invention, a hydrosilylation catalyst can be additionally used as necessary.

  The curing time can be appropriately selected depending on the curing temperature, the amount of hydrosilylation catalyst to be used and the amount of hydrosilyl group, and other combinations of the composition of the present application. Is carried out for 10 minutes to 16 hours, a good cured product can be obtained.

  Specifically, the polysiloxane composition in the present invention can be used, for example, by being injected or applied to a predetermined mold. It is possible to obtain a cured product having excellent impact resistance by curing under the above-mentioned curing conditions after injection or application.

  In addition to the essential components described above, the polysiloxane composition used in the present invention may contain a filler such as silica, pulverized quartz, calcium carbonate, carbon, etc., as necessary, within a range that does not interfere with the effects of the present invention. It may be added.

  In addition, the polysiloxane composition of the present invention includes various additives such as an adhesion-imparting agent, a colorant, and a heat resistance improver, a reaction control agent, a release agent, or a dispersant for a filler as necessary. It can be optionally added.

  Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like.

In order to make the polysiloxane composition of the present invention flame-retardant and fire-resistant, known additives such as titanium dioxide, manganese carbonate, Fe ₂ O ₃ , ferrite, mica, glass fiber, glass flakes are added. May be. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

  In the polysiloxane composition used in the present invention, the above-mentioned components are uniformly mixed using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and subjected to heat treatment as necessary. Can be obtained.

  The polysiloxane composition of the present invention can be used as a molded article. As a molding method, any method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, liquid injection molding, and cast molding can be used.

  The molded product obtained from the polysiloxane composition according to the present invention is excellent in heat resistance and light resistance.

  The polysiloxane composition of the present invention can be used as a composition for optical materials. The optical material mentioned here refers to general materials used for the purpose of allowing light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material.

  Specific uses of the modified product and composition obtained in the present invention include color filters, resist materials, substrate materials in the field of liquid crystal displays, passivation films, light guide plates, prism sheets, deflection plates, retardation plates, visual fields Examples include peripheral materials for liquid crystal display devices such as a liquid crystal film such as a corner correction film, an adhesive, and a polarizer protective film.

  In addition, color PDP (plasma display) sealants, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitute materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED element mold material used in the device, front glass protective film, front glass substitute material, adhesive, substrate material for plasma addressed liquid crystal (PALC) display, light guide plate, prism sheet, deflector plate, retardation plate, Viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various film substrates and front glass in field emission display (FED) Protective films, front glass substitute material, adhesives.

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Examples include pickup lenses, protective films, sealants, and adhesives.

  In the field of optical equipment, examples include still camera lens materials, viewfinder prisms, target prisms, viewfinder covers, and light receiving sensor sections. In addition, a photographing lens and a viewfinder of a video camera are exemplified. Moreover, the projection lens of a projection television, a protective film, a sealing agent, an adhesive agent, etc. are illustrated. Examples are materials for lenses of optical sensing devices, sealants, adhesives, and films.

  In the field of optical components, fiber materials, lenses, waveguides, element sealants, adhesives and the like around optical switches in optical communication systems are exemplified. Examples include optical fiber materials, ferrules, sealants, adhesives and the like around the optical connector. Examples of optical passive components and optical circuit components include lenses, waveguides, LED element sealants, adhesives, and the like. Examples include substrate materials, fiber materials, element sealants, adhesives, and the like around an optoelectronic integrated circuit (OEIC).

  In the field of optical fibers, examples include sensors for industrial use such as lighting and light guides for decorative displays, displays and signs, and optical fibers for communication infrastructure and for connecting digital devices in the home.

  Examples of the semiconductor integrated circuit peripheral material include resist materials for microlithography for LSI and VLSI materials.

  In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Examples include rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, and glass substitutes. Moreover, the multilayer glass for rail vehicles is illustrated. Further, examples thereof include a toughness imparting agent for aircraft structural materials, engine peripheral members, wireness for protection and binding, and corrosion-resistant coating.

  In the construction field, interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials are exemplified. In agriculture, a house covering film is exemplified.

  Next-generation DVDs, organic EL element peripheral materials, organic photorefractive elements, light-amplifying elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, etc. Examples thereof include fiber materials, element sealants, and adhesives.

  Next, although the composition of this invention is demonstrated in detail based on an Example, this invention is not limited only to these Examples.

<Test method>
(Light transmittance)
Using a UV-visible spectrophotometer V-560 (manufactured by JASCO Corporation), the light transmittance at a wavelength of 700 nm was measured under the conditions of temperature 20 ° C./humidity 50%.

(Impact resistance test)
Using a hydroshot (manufactured by Shimadzu Corporation), the energy for punching an 8 cm square, 4 mm thick plate-like molded body was measured in an atmosphere at 25 ° C.

(Production Example 1)
1083 g of tetraethoxysilane was added to 1262 g of a 48% choline aqueous solution and vigorously stirred at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1000 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.

  While vigorously stirring a solution of 537 g of dimethylvinylchlorosilane, 645 g of trimethylchlorosilane, and 1942 mL of hexane, the methanol solution was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, the produced solid matter is washed by vigorously stirring in methanol and filtered to obtain a polyhedral polysiloxane compound (hereinafter referred to as compound) in which eight silicon atoms have a cage-like three-dimensional structure through a siloxane bond. (Abbreviated as A) was obtained as a white solid.

It was confirmed by ¹ H-NMR that the obtained compound was a polyhedral polysiloxane compound having a dimethylvinylsilyl group and a trimethylsilyl group introduced at a ratio of 3: 5.

(Production Example 2)
40 g of the compound A obtained in Production Example 1 and 9.25 μL of a platinum vinylsiloxane complex xylene solution (Pt-VTSC-3X, manufactured by Umicore Precious Metals Japan) were dissolved in 80 g of toluene. The solution thus obtained was slowly dropped into a solution prepared by dissolving 61.87 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane in 62 g of toluene. The mixture was reacted at 95 ° C. for 3 hours and cooled to room temperature.

After completion of the reaction, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane added in excess with a solvent is distilled off to obtain a modified polyhedral polysiloxane (hereinafter referred to as “polyhedral polysiloxane”). 62g) was obtained. The obtained compound is a transparent liquid, the vinyl group disappears by ¹ H-NMR, and is derived from 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane. It was confirmed that SiH groups were introduced.

(Production Example 3)
While vigorously stirring a solution of 161 g of dimethylvinylchlorosilane, 31 g of dimethyldichlorosilane and 242 mL of hexane, 500 mL of a methanol solution obtained in the same manner as in Production Example 1 was slowly added dropwise. After the completion of the dropwise addition, the reaction is allowed to proceed for 1 hour, and then the organic layer is extracted, filtered using Celite (manufactured by Wako Pure Chemical Industries, Ltd.), and the filtrate is concentrated, whereby 8 silicon atoms are caged by siloxane bonds. 83 g of a polyhedral polysiloxane compound (hereinafter referred to as Compound C) having a three-dimensional structure was obtained as a viscous solid. The resulting compound is introduced dimethyl vinyl silyl group Si atoms of the cage structure, that part is polyhedral polysiloxane compound is linked to a separate cage structure by butyldimethylsilyl group, ¹ Confirmed by 1 H-NMR.

(Production Example 4)
23 g of Compound C23 g obtained in Production Example 3 and 13.33 μL of a platinum vinylsiloxane complex xylene solution (manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) were dissolved in 55 g of toluene. The solution thus obtained was slowly dropped into a solution in which 82.30 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane was dissolved in 82 g of toluene. The mixture was reacted at 95 ° C. for 2 hours and cooled to room temperature.

After completion of the reaction, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane added in excess with a solvent is distilled off to obtain a modified polyhedral polysiloxane (hereinafter referred to as “polyhedral polysiloxane”). 57.08 g) (referred to as compound D). The obtained compound is a transparent liquid, the vinyl group disappears by ¹ H-NMR, and is derived from 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane. It was confirmed that SiH groups were introduced.

Example 1
To the compound D20 g obtained in Production Example 4, 4.93 g of a linear polydimethylsiloxane containing a vinyl group at the terminal (LS-7250, manufactured by Shin-Etsu Silicone, molecular weight 184), a vinyl group-containing polysiloxane having a three-dimensional structure ( MQV-7, Clariant, vinyl group content 3.5 mol / kg, 8.21 g) was added to prepare a polysiloxane composition.

  The obtained polysiloxane composition is poured into a mold and heated at 60 ° C. for 3 hours, 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 1 hour. And cured to obtain a molded body having a thickness of 4 mm, and an impact resistance test was conducted. The composition was poured into a 1 mm thick mold and heated and cured under the same conditions to obtain a 1 mm thick molded article for evaluation, and a light transmittance test was performed. The results are shown in Table 1.

(Comparative Example 1)
To the compound B (14.10 g) obtained in Production Example 2, 2.09 g of a linear polydimethylsiloxane having a vinyl group at its terminal (DMS-V03, manufactured by AMAX, molecular weight 800), a vinyl group-containing polysiloxane having a three-dimensional structure (MQV-7, Clariant Inc., vinyl group content 3.5 mol / kg) 13.95 g was added to prepare a polysiloxane composition.

  The obtained polysiloxane composition is poured into a mold and heated at 60 ° C. for 3 hours, 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 1 hour. And cured to obtain a molded body having a thickness of 4 mm, and an impact resistance test was conducted. The composition was poured into a 1 mm thick mold and heated and cured under the same conditions to obtain a 1 mm thick molded article for evaluation, and a light transmittance test was performed. The results are shown in Table 1.

  As described above, the composition obtained from the modified polyhedral polysiloxane of the present invention is excellent in transparency, heat resistance and impact resistance. Further, since it can be handled as a liquid composition, it is clear that it is excellent in workability and moldability.

Claims (7)

Formula [XR ₂ SiO—SiO _3/2 ] _a [XR ₂ SiO— (R ₂ SiO) _m —SiO _3/2 ] _b [R ′ — (R ₂ SiO) _n —SiO _3/2 ] _c (a˜ c is an integer of 0 or 1 or more, a + b + c is an integer of 6 to 24, b + c is an integer of 1 or more, m, n is an integer of 1 or more; R is an alkyl group or an aryl group, R ′ is another polyhedral polysiloxane; X is a hydrogen atom or an alkenyl group, and may be the same or different). The polyhedral polysiloxane compound (a) is obtained by hydrosilylating a siloxane compound (b) containing a hydrosilyl group or an alkenyl group, and is a liquid at 20 ° C. A hexane modified product,
A modified polyhedral polysiloxane in which the siloxane compound (b) is a cyclic siloxane having a hydrosilyl group or an alkenyl group, or a linear siloxane having a hydrosilyl group or an alkenyl group . The modified polyhedral polysiloxane according to claim 1, wherein the modified polyhedral polysiloxane has at least three hydrosilyl groups or alkenyl groups in the molecule. The polyhedral polysiloxane according to claim 1 or 2, wherein the polyhedral polysiloxane compound (a) is obtained by reacting a silicate having a polyhedral structure with a mixture of monochlorosilane and dichlorosilane. Modified siloxane. A polysiloxane-based composition comprising the modified polyhedral polysiloxane according to any one of claims 1 to 3. The polysiloxane composition according to claim 4, comprising a curing agent containing at least one alkenyl group or hydrosilyl group. The polysiloxane composition according to claim 5, wherein the curing agent contains polysiloxane having a molecular weight of less than 1000 as an essential component. The polysiloxane composition according to any one of claims 4 to 6, comprising a hydrosilylation catalyst.